Conversion of hydrocarbons in the presence of cracking catalyst containing barium peroxide



'My invention relates v v "catalytic conversion of hydrocarbons such 'as Patented Oct. 30,1951

UNITED ris-TENT OFFICE 2,573,483 I V 1 CONVERSION oF nYpRocAaBoNs qN THE PRESENCE OF. 'CRACKINGLOATALY'STCON' TAINING-BARIUM PEROXIDE 1 emrdfl iise isd fml li n to Sinclair-Refining GompanyfNewYork N. Y.', a 'cdrporationfofMaine renewing 'ga'iiplica o m 26 .1947,

' 1 "seriaii No. 757,310

to 'improvement'sdn' the petroleum and other mineral 'oil'stocksto -pro' versions with a new and improved crackingcatalyst comprising barium peroxide when liberates oxygen to act as a homogeneous catalyst.

iii-Claims (01.196 52) duce gasoline of'high anti-knock value, 'andmore particularly to the carrying outo'f such con- An important feature of my process comprises an improved catalyst including a silica-alumina or silica-zirconia type material crackingcatalysts in which barium peroxide or oxide is incorporated. At cracking temperatures it is believed that the barium peroxide acts as a proasa catalyst in cracking-hydrocarbon oil's'or' indirectly to promote the optimum activity of the silica or alumina type catalysts.

The features of my invention may be illustrated in connection with a specific example in which barium peroxide is mixed with a catalytic material comprising a silica-alumina composition of the type now employed in catalytic cracking operations. The mixtur includes approximately 10% by weight of barium peroxide and is processed by conventionally known procedure to form the catalytic mixture into porous granular particles, pellets or extruded shapes, or into a fluid type catalyst form. In any case the catalyst as prepared for use advantageously has a very extensive active surface so that the majority of the barium oxide content will be available. I

This catalyst, having approximately the composition referred to above is used in the cracking of a gas oil, for example, at a, temperature of from 915 to 1015 F., in a reaction zone. The catalyst if in finely divided form may be used as a fluid type catalyst, or if in pellet, extruded or coarse granular form it may be used as a moving bed in a vertical type reactor or as a static bed.

In the reactor the barium peroxide tends to keep th catalyst mass in active state and liberates oxygen which not only effects its activation, but acts as a homogeneous catalyst in the breaking of hydrocarbon molecules. The cracking operation is advantageously carried out at relatively low pressure of from slightly more than atmospheric to approximately 100 lbs. per'sq. inch, about lbs. per sq. inch being suitable, so as to facilitate the liberation'of the oxygenfrdrh barium peroxide. The oil stockto be craeke heated in a conventional" type" still, passedirito the'reactionchamber, and the resulting 'crac Productsent toa' conventional recovery jsys n including a'fractionating' tower; condenseriand productreceivers. v i ii An importantfeature of my'proces's'relate the regeneration or"revivification of the catalyst since the barium" peroxide is" reducedto barium oxide in thecrackingoperation. The catalyst," if 'n'o't used'in'a'fixed bedor beds; is therefore ith"- drawn from the reactioncliamber and regenei' ated by hydrogenation at temperaturesof' 'about '1 'l00 'F. by passing the catalyst'in' intimate con tact with hydrogen or hydrogen 'cont'aining'gas so as to hydrogenate the tarry materials which are deposited on the catalyst in'the reaction chamber, these materials'being made b hydrogenation and removed in 'the'hydrogenatmn step. After hydrogenating the catalyst, it is advantageously passed into a chamber at a somewhat lower temperature and contacted with air i or oxygen, free of other materials, which would react with barium oxide or peroxide. Oxygen converts the barium oxide to barium peroxide. The conversion of the BaO is advantageously effected by cooling the catalyst in and with a stream of air or oxygen containing gas. In any case, the contact with air or oxygen should be well below 1400" F. and advantageously at temperatures in the range-of from 500 to 700 F. At temperatures below 1400 F. barium oxide takes up oxygen to form barium peroxide (BaOz). The catalyst is now ready for reuse in the process.

In the manufacture of composition catalysts in which barium peroxide is employed as an ingredient of the mixture, the BaOz or BaO may be used in a percentage range of from 5% to 25% by weight. With the relatively inexpensive silicaalumina type catalysts, relatively low percentages are advantageously employed. However, in the regeneration of such catalysts, th operation is preferably conducted to remove adsorbed tarry or coke forming constituents without burning the catalyst as in conventional regeneration procedures, to avoid converting the BaO to unreactive compounds. In some cases the adsorbed materials of the spent catalyst may be removed by means of solvents. The solvent treatment, for example with benzene or naphtha, and hydrogenation, may be combined as a series of steps in any order. The barium peroxide may be combined with any of the metal oxide, clay. silica,

mixture of barium oxide and barium peroxide' may be used in making up the catalyst; since the barium oxide content of the catalyst maybe readily converted to the peroxide by contacting the catalyst with oxygen at the temperatures referred to above.

I claim:

1. The improvement in the cracking of higher 4 ucts from the cracking operation, regenerating the used catalyst to preserve the barium oxide in the spent catalyst, and reusing the regenerated catalyst in the cracking operation, the regenerating operation comprising thestep of first removing .the carbonaceous material deposited on'the catalyst during the cracking operation and then a subsequent step of converting the barium oxide to barium peroxide.

3.-The improvement in the cracking of higher boiling hydrocarbon oils for the production of gasoline therefrom, which comprises subjecting the oil to a cracking temperature in the presence of a cracking catalyst having intimately admixed therewith a substantial proportion of barium peroxide, recovering the converted products from boiling hydrocarbon oils for the production of gasoline therefrom, which comprises subjecting the oil to a cracking temperature in the presence pf acracking catalyst having intimatelyadmixed therewith a substantial proportionuof. barium peroxide, recovering theconverted products from the cracking operation, regenerating the used catalyst under, conditions adapted to preserve the barium oxide in the spent catalyst, the. regenerating operation including the steps of removing any carbonand tarry constituent from the catalyst by hydrogenation and thereafter cooling the catalyst in a stream of gas comprising oxygen to convert the bariumoxide of the catalyst to barium-peroxide, and reusing the regenerated catalyst in the cracking operation. a a 2. The improvement in the cracking of higher boiling hydrocarbon oils for the production of gasoline therefrom, which comprises subjecting the oil to a cracking temperaturerin the presence of a crackingcatalyst having intimately admixed ,therewith a substantial proportion of barium peroxide, recovering the converted prodthe cracking operation, regenerating the used catalyst to preserve the barium oxide in the spent catalyst, and reusing the regenerated catalyst in the cracking operation, the regenerating operation comprising the step of first removingthe carbonaceous material deposited on the catalyst during the cracking operation and then a-subsequentstep of converting the barium oxide to barium peroxide by reacting the barium oxide with oxygen at temperatures in the range of 500 to 700 F.

LEONARD EUGENE OLSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number 2,419,342 Edson et al Apr. 22, 1947 

1. THE IMPROVEMENT IN THE CRACKING OF HIGHER BOILING HYDROCARBON OILS FOR THE PRODUCTION OF GASOLINE THEREFROM, WHICH COMPRISES SUBJECTING THE OIL TO A CRACKING TEMPERATURE IN THE PRESENCE OF A CRACKING CATALYST HAVING INTIMATELY ADMIXED THEREWITH A SUBSTANTIAL PROPORTION OF BARIUM PEROXIDE, RECOVERING THE CONVERTED PRODUCTS FROM THE CRACKING OPERATION, REGENERATING THE USED CATALYST UNDER CONDITIONS ADAPTED TO PRESERVE THE BARIUM OXIDE IN THE SPENT CATALYST, THE REGENERATING OPERATION INCLUDING THE STEPS OF REMOVING ANY CARBON AND TARRY CONSTITUENT FROM THE CATALYST BY HYDROGENATION AND THEREAFTER COOLING THE CATALYST IN A STREAM OF GAS COMPRISING OXYGEN TO CONVERT THE BARIUM OXIDE OF THE CATALYST TO BARIUM PEROXIDE, AND REUSING THE REGENERATED CATALYST IN THE CRACKING OPERATION. 